Fluorescent brighteners, methods of preparation thereof, fluorescent brightener compositions, and methods of preparation and uses thereof

ABSTRACT

A compound of Formula (I) 
     
       
         
         
             
             
         
       
     
     wherein R 1 , R 2 , and R 3  are independently at each occurrence hydrogen, a halogen, a cyano functionality, a C 1 -C 20  aliphatic functionality, a C 3 -C 10  cycloaliphatic functionality or a C 3 -C 20  aromatic functionality, with the proviso that R 2  and R 3  are not hydrogen when R 1  is a methyl or hydrogen; R 4  and R 5  are independently at each occurrence hydrogen, a halogen, a cyano functionality, a C 1 -C 20  aliphatic functionality, a C 3 -C 10  cycloaliphatic functionality or a C 3 -C 10  aromatic functionality; R 7  and R 8  are independently at each occurrence, a halogen, a cyano functionality, a C 1 -C 20  aliphatic functionality, a C 3 -C 10  cycloaliphatic functionality or a C 3 -C 10  aromatic functionality; R 6  is a C 2 -C 20  aliphatic functionality, a C 3 -C 10  cycloaliphatic functionality or a C 3 -C 20  aromatic functionality; and “n” and “m” are each independently integers having a value of 0 to 3.

BACKGROUND OF THE INVENTION

This disclosure relates to fluorescent brighteners. More particularlythe disclosure relates to fluorescent brighteners, methods of preparingthe fluorescent brighteners, compositions comprising the fluorescentbrighteners, in particular polymer compositions comprising thefluorescent brighteners, and uses thereof.

Fluorescent brighteners, also known as fluorescent whitening agents,fluorescent whiteners, optical brighteners, and optical whiteners, areadditives that alter the visual properties of polymers. Fluorescentbrighteners are colorless to weakly colored organic compounds. When insolution, applied to a substrate, or combined with a polymer, theyabsorb primarily ultraviolet light in the 300 to 400 nanometer (nm)range. Most of the absorbed energy is then re-emitted as visibleviolet-to-blue fluorescent light in the 400 to 500 nm range. Fluorescentbrighteners thus help to mask inherent yellowness in discolored polymersand impart unique, robust color to specialty plastic products.

There are very few fluorescent brighteners exhibiting high Tg values. Inaddition, many fluorescent brighteners decompose at temperaturescommonly used to process polymers. One high Tg fluorescent brightener is2,2′-(2,5-thiophenediyl) bis[5-(1,1-dimethylethyl)]-benzoxazole, (CASNo. [7128-64-5]) available from Ciba under the trade name UVITEX®-OB.Nonetheless, there remains a need in the art for fluorescent brightenersthat have a high Tg to enable their use in a wide variety of polymers,especially thermoplastic polymers.

SUMMARY OF THE INVENTION

Disclosed herein is a compound of Formula (I)

wherein R¹, R², and R³ are independently at each occurrence hydrogen, ahalogen, a cyano functionality, a C₁-C₂₀ aliphatic functionality, aC₃-C₁₀ cycloaliphatic functionality, or a C₃-C₂₀ aromatic functionality,with the proviso that R² and R³ are not hydrogen when R¹ is a methyl orhydrogen; R⁴ and R⁵ are independently at each occurrence hydrogen, ahalogen, a cyano functionality, a C₁-C₂₀ aliphatic functionality, aC₃-C₁₀ cycloaliphatic functionality, or a C₃-C₁₀ aromatic functionality;R⁷ and R⁸ are independently at each occurrence, a halogen, a cyanofunctionality, a C₁-C₂₀ aliphatic functionality, a C₃-C₁₀ cycloaliphaticfunctionality, or a C₃-C₁₀ aromatic functionality; R⁶ is a C₂-C₂₀aliphatic functionality, a C₃-C₁₀ cycloaliphatic functionality, or aC₃-C₂₀ aromatic functionality; and “n” and “m” are each independentlyintegers having a value of 0 to 3.

In one embodiment a process for preparing a compound of Formula (I)comprises reacting an anhydride compound of Formula (IV) with an anilinecompound of Formula (V)

in the presence of a first solvent to provide a compound of Formula (VI)

reacting the compound of Formula (VI) with a hydroxy compound of Formula(VII)

R⁶—OH  (VII)

in the presence of a base and a second solvent to provide a compound ofFormula (I)

wherein R¹, R², and R³ are independently at each occurrence hydrogen, ahalogen, a cyano functionality, a C₁-C₂₀ aliphatic functionality, aC₃-C₁₀ cycloaliphatic functionality, or a C₃-C₂₀ aromatic functionality,with the proviso that R² and R³ are not hydrogen when R¹ is a methyl orhydrogen;R⁴ and R⁵ are independently at each occurrence hydrogen, a halogen, aC₁-C₂₀ aliphatic functionality, a C₃-C₁₀ cycloaliphatic functionality,or a C₃-C₁₀ aromatic functionality;R⁷ and R⁸ are independently at each occurrence a halogen, a C₁-C₂₀aliphatic functionality, a C₃-C₁₀ cycloaliphatic functionality, or aC₃-C₁₀ aromatic functionality;R⁶ is a C₂-C₂₀ aliphatic functionality, a C₃-C₁₀ cycloaliphaticfunctionality, or a C₃-C₂₀ aromatic functionality;X is a halogen selected from chlorine, bromine or iodine; and“n” and “m” are each independently integers having a value of 0 to 3.

Also disclosed herein are compositions comprising the compound ofFormula (I), methods of making the compositions, and articles comprisingthe composition comprising the compound of Formula (I).

The above-described and other features are exemplified by the followingdetailed description.

DETAILED DESCRIPTION OF THE INVENTION

Disclosed herein are compounds having high Tg and that in someembodiments may be used as fluorescent brighteners.

The singular forms “a”, “an” and “the” include plural referents unlessthe context clearly dictates otherwise. All ranges disclosed herein areinclusive of the endpoint and independently combinable (for exampleranges of “up to 25 weight (wt.) percent, with 5 wt. percent to 20 wt.percent desired,” is inclusive of the endpoints and all intermediatevalues of the ranges of “5 wt. percent to 25 wt. percent”).

The Modifier “about” Used in Connection with a Quantity is Inclusive ofthe stated value and has the meaning dictated by the context (forexample, includes the degree of error associated with measurement of theparticular quantity).

“BPA” is herein defined as bisphenol A, and is also known as2,2-bis(4-hydroxyphenyl)propane, 4,4′-isopropylidenediphenol, andp,p-BPA.

Unless otherwise specified, the term “cycloaliphatic functionality”designates cyclic aliphatic functionalities having a valence of at leastone, and comprising an array of atoms which is cyclic but which is notaromatic. The cycloaliphatic functionality may include heteroatoms suchas nitrogen, sulfur, selenium, silicon, and oxygen, or may be composedexclusively of carbon and hydrogen. A “cycloaliphatic functionality” maybe linked via the cyclic group or via another group on the cyclic group.For example, a cyclohexylmethyl group (C₆H₁₁CH₂—) is a cycloaliphaticfunctionality that comprises a cyclohexyl ring (the array of atoms whichis cyclic but which is not aromatic) and a methylene group (thenoncyclic component). A “cycloaliphatic moiety” may further beunsubstituted or substituted, i.e., comprising one or more noncycliccomponents, including functional groups such as alkyl groups, alkenylgroups, alkynyl groups, haloalkyl groups, halogen(s), conjugated dienylgroups, alcohol groups, ether groups, carboxylic acid groups, acylgroups (for example carboxylic acid derivatives such as esters andamides), amine groups and nitro groups, provided that the functionalgroup(s) do not substantially adversely impact the intended function ofthe compound. For example, the 4-methylcyclopent-1-yl group is a C₆cycloaliphatic functionality comprising a methyl group, wherein themethyl group is an alkyl functional group. Similarly, the2-nitrocyclobut-1-yl group is a C₄ cycloaliphatic functionalitycomprising a nitro group, wherein the nitro group is a functional group.Exemplary cycloaliphatic functionalities include cyclopropyl,cyclobutyl, 1,1,4,4-tetramethylcyclobutyl, piperidinyl,2,2,6,6-tetramethylpiperidinyl, cyclohexyl, and cyclopentyl.

As used herein, the term “aromatic functionality” refers to an array ofatoms having a valence of at least one, and comprising at least onearomatic group. The array of atoms comprising the at least one aromaticgroup may include heteroatoms such as nitrogen, sulfur, selenium,silicon, and oxygen, or may be composed exclusively of carbon andhydrogen. As used herein, the term “aromatic functionality” includes butis not limited to phenyl, pyridyl, furanyl, thienyl, naphthyl,phenylene, and biphenyl functionalities. The aromatic functionality mayalso include nonaromatic components. For example, a benzyl group is anaromatic functionality that comprises a phenyl ring (the aromatic group)and a methylene group (the nonaromatic component). Similarly atetrahydronaphthyl functionality is an aromatic functionality comprisingan aromatic group (C₆H₃) fused to a nonaromatic component —(CH₂)₄—. An“aromatic functionality” may further be unsubstituted or substitutedwith a wide range of functional groups such as alkyl groups, haloalkylgroups, haloaromatic groups, halogens, alcohol groups, ether groups,carboxylic acid groups, acyl groups (for example carboxylic acidderivatives such as esters and amides), amine groups and nitro groups,provided that the functional group(s) do not substantially adverselyimpact the intended function of the compound. For example, the4-methylphenyl functionality is a C₇ aromatic functionality comprising amethyl group, wherein the methyl group is an alkyl functional group.Similarly, the 2-nitrophenyl group is a C₆ aromatic functionalitycomprising a nitro group, wherein the nitro group is a functional group.Exemplary aromatic functionalities include, but are not limited tophenyl, 4-trifluoromethylphenyl, 4-chloromethylphen-1-yl,3-trichloromethylphen-1-yl (3-CCl₃Ph-), 4-(3-bromoprop-1-yl)phen-1-yl(4-BrCH₂CH₂CH₂Ph-), 4-aminophen-1-yl (4-H₂NPh-),4-hydroxymethylphen-1-yl (4-HOCH₂Ph-), 4-methylthiophen-1-yl(4-CH₃SPh-), 3-methoxyphen-1-yl, 2-nitromethylphen-1-yl (2-NO₂CH₂Ph-),and naphthyl.

As used herein the term “aliphatic functionality” refers to an organicfunctionality having at least one carbon, a valence of at least one, andconsisting of a linear or branched array of atoms that is not cyclic.The array of atoms comprising the aliphatic functionality may includeheteroatoms such as nitrogen, sulfur, silicon, selenium, and oxygen ormay be composed exclusively of carbon and hydrogen. An “aliphaticfunctionality” may be unsubstituted or substituted with a wide range offunctional groups such as alkyl groups, haloalkyl groups, halogens,alcohol groups, ether groups, carboxylic acid groups, acyl groups (forexample carboxylic acid derivatives such as esters and amides), aminegroups, and nitro groups, provided that the functional group(s) do notsubstantially adversely impact the intended function of the compound.For example, the 4-methylpent-1-yl is a C₆ aliphatic functionalitycomprising a methyl group, wherein the methyl group is a functionalgroup which is an alkyl group. Similarly, the 4-nitrobut-1-yl group is aC₄ aliphatic functionality comprising a nitro group, wherein the nitrogroup is a functional group. Exemplary aliphatic functionalitiesinclude, but are not limited to methyl, ethyl, propyl, isopropyl, butyl,isobutyl, pentyl, isopentyl, trifluoromethyl, bromodifluoromethyl,chlorodifluoromethyl, chloromethyl, trichloromethyl, bromoethyl,2-hexyl, hexamethylene, hydroxymethyl (—CH₂OH), mercaptomethyl (—CH₂SH),methylthio (—SCH₃), methylthiomethyl (—CH₂SCH₃), methoxy,methoxycarbonyl (CH₃OCO—), nitromethyl (—CH₂NO₂) and thiocarbonyl.

In one embodiment compounds of Formula (I) are disclosed,

wherein R¹, R², and R³ are independently at each occurrence hydrogen, ahalogen, a cyano functionality, a C₁-C₂₀ aliphatic functionality, aC₃-C₁₀ cycloaliphatic functionality, or a C₃-C₂₀ aromatic functionality,with the proviso that R² and R³ are not hydrogen when R¹ is a methyl orhydrogen; R⁴ and R⁵ are independently at each occurrence hydrogen, ahalogen, a cyano functionality, a C₁-C₂₀ aliphatic functionality, aC₃-C₁₀ cycloaliphatic functionality, or a C₃-C₁₀ aromatic functionality;R⁷ and R⁸ are independently at each occurrence a halogen, a cyanofunctionality, a C₁-C₂₀ aliphatic functionality, a C₃-C₁₀ cycloaliphaticfunctionality, or a C₃-C₁₀ aromatic functionality; R⁶ is a C₂-C₂₀aliphatic functionality, a C₃-C₁₀ cycloaliphatic functionality, or aC₃-C₂₀ aromatic functionality; and “n” and “m” are each independentlyintegers having a value of 0 to 3.

In one embodiment, R¹, R⁴, and R⁵ are each hydrogen, R² and R³ are eacha C₂-C₆ aliphatic functionality that can be the same or different, R⁷and R⁸ are independently at each occurrence a halogen, a cyanofunctionality, or a C₁-C₆ aliphatic functionality, and n and m are each0 to 3.

In a specific embodiment R¹, R⁴, and R⁵ are hydrogen, R² and R³ are botha C₃ aliphatic functionality, R⁶ is a C₂-C₄ aliphatic functionality or aC₆₋₁₈ aromatic functionality and n and m are each 0.

In one embodiment the compound is of Formula (II) or Formula (III)

wherein in Formula (II) “p” has a value of 2 to 4. The compound ofFormula (II) when “p” is 2 to 4 may be referred to as2-(2,6-diisopropylphenyl)-6-(2-hydroxyethoxy)-benzo[de]isoquinoline-1,3-dione;2-(2,6-diisopropylphenyl)-6-(3-hydroxypropoxy)-benzo[de]isoquinoline-1,3-dioneand2-(2,6-diisopropyl-phenyl)-6-(4-hydroxy-butoxy)-benzo[de]isoquinoline-1,3-dione,respectively, and the compound of Formula (III) may be referred to as2-(2,6-diisopropylphenyl)-6-[4-(1-methyl-1-phenylethyl)-phenoxy]-benzo[de]isoquinoline-1,3-dione.

In one embodiment a process for making the fluorescent brightenercompound of Formula (I) is as follows. An anhydride compound of Formula(IV), wherein X is a halogen, is reacted with an aniline compound ofFormula (V)

in the presence of a first solvent to provide a compound of Formula (VI)wherein R¹, R², R³, R⁴, R⁵, R⁷, R⁸, “n,” and “m” have the same meaningas defined above.

Suitable anhydride compounds of Formula (IV) include4-bromo-1,8-naphthalic anhydride, 4,5-dibromo-1,8-naphthalic anhydride,2-benzoyl-4-bromo-1,8-naphthalic anhydride,2-acetyl-4-bromo-1,8-naphthalic anhydride,2-ethyl-4-bromo-1,8-naphthalic anhydride, 4,6-dibromo-1,8-naphthalicanhydride, and combinations comprising at least one of the foregoinganhydrides.

Suitable aniline compounds of Formula (V) include2,6-diisopropylaniline, 4-propylaniline, 4-iodo-2-methylaniline,4-bromo-3-methylaniline, 3-bromo-2,4,6-trimethylaniline,2-bromo-4-chloro aniline, 4-(1H-imidazol-1-yl)-aniline, and combinationscomprising at least one of the foregoing aniline compounds.

The amount of the aniline compound of Formula (V) employed in thereaction can be about 1.0 mole to about 3.0 moles per mole of anhydridecompound of Formula (IV) employed. Within this range the amount may begreater than or equal to 1.2 moles, or, more specifically, greater thanor equal to about 1.5 moles. Also within this range the amount may beless than or equal to about 2.5 moles, or, more specifically less thanor equal to about 2.0 moles.

Specific examples of suitable first solvents that can be employed in thereaction of the anhydride compound of Formula (IV) with the anilinecompound of Formula (V) to produce the compound of Formula (VI) include,but are not limited to acetic acid, propionic acid, butanoic acid,ethanol, methanol, propanol, iso-propanol, butanol, iso-butanol,toluene, xylene, dichloromethane, dichloroethane, chloroform,chlorobenzene, ortho-dichlorobenzene, trichlorobenzene,dimethylformamide, diethylacetamide, tetrahydrofuran, dimethylsulfoxide,or combinations of one or more of the foregoing solvents. In oneembodiment the solvent employed comprises acetic acid. In certainembodiments the amount of solvent employed in the reaction of theanhydride compound of Formula (IV) with the aniline compound of Formula(V) can be about 10 moles to about 50 moles liters per mole of anhydridecompound of Formula (IV). Within this range the amount may be greaterthan or equal to about 15 moles, or, more specifically, greater than orequal to about 20 moles. Also within this range the amount may be lessthan or equal to about 40 moles, or, more specifically less than orequal to about 30 moles.

The temperature at which the reaction of the anhydride compound ofFormula (IV) with the aniline compound of Formula (V) takes place may beabout 80° C. to about 180° C. Within this range the temperature may begreater than or equal to about 90° C., or, more specifically, greaterthan or equal to about 100° C. Also within this range the temperaturemay be less than or equal to about 160° C., or, more specifically, lessthan or equal to about 150° C. The time taken for the reaction of theanhydride compound of Formula (IV) with the aniline compound of Formula(V) can be about 3 hours to about 20 hours. Within this range the timemay be greater than or equal to about 5 hours, or, more specifically,greater than or equal to about 10 hours. Also within this range the timemay be less than or equal to about 18 hours, or, more specifically, lessthan or equal to about 15 hours.

The compound of Formula (VI) is reacted with a hydroxy compound ofFormula (VII)

R⁶—OH  (VII)

wherein R⁶ is as described above, in the presence of a base and a secondsolvent to provide a compound of Formula (I) as described above.

Suitable hydroxy compounds of Formula (VII) include, but are not limitedto, 1,2-ethylene diol, 1,3-propylene diol, 1,4-butane diol, 4-cumylphenol, 1,6-hexane diol, 1,7-heptanediol, 1,8-octane diol,1,4-cyclohexane diol, 1,2-cyclohexane diol, and combinations comprisingat least one of the foregoing hydroxy compounds.

The amount of hydroxy compound of Formula (VII) employed in the reactioncan be 1 mole to 5 moles per mole of compound of Formula (VI). Withinthis range the amount may be greater than or equal to about 2 moles, or,more specifically, greater than or equal to about 2.5 moles. Also withinthis range the amount may be less than or equal to about 4.5 moles, or,more specifically, less than or equal to about 4 moles.

Suitable bases include but are not limited to alkali metal hydroxides,alkali metal carbonates, alkaline earth metal hydroxides, or alkalineearth metal carbonates. Specific alkali metal hydroxides or alkalineearth metal hydroxides include but are not limited to sodium hydroxide,lithium hydroxide, potassium hydroxide, rubidium hydroxide, calciumhydroxide, sodium carbonate, potassium carbonate, and magnesiumhydroxide.

In one embodiment a catalyst may be employed in reaction of the compoundof Formula (VI) with the hydroxide of Formula (VII). Without being boundto theory it is believed that use of the catalyst will help to increasethe speed of the reaction, thereby decreasing reaction time. Suitablecatalysts include, but are not limited, to phase transfer catalysts suchas tetrabutylammonium bromide, tetrabutylammonium chloride,tetrabutylammonium fluoride trihydrate, tetrabutylammonium hydrogensulfate, tetrabutylammonium iodide, tetrabutylammonium thiocyanate,tetrabutylammonium tetrafluoroborate, benzyltributylammonium chloride,benzyltriethylammonium chloride, benzyltrimethylammonium bromide,benzyltrimethylammonium chloride, hexadecyltrimethylammonium bromide,hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium hydrogensulfate, methyltrioctadecylammonium bromide, methyltrioctylammoniumbromide, methyltrioctylammonium chloride, tetraethylammonium bromide,tetraethylammonium chloride, tetraethylammonium fluoride dihydrate,tetraethylammonium hexafluorophosphate, tetraethylammoniumtetrafluoroborate, tetrahexylammonium hydrogen sulfate,tetramethylammonium bromide, tetramethylammonium chloride,tetraoctylammonium bromide, tetraoctylammonium chloride, polyethyleneglycol, hexamethylphosphoramide, tributylmethylphosphonium chloride,tributylmethylphosphonium chloride, hexyltributylphosphonium bromide,tributylmethylammonium chloride, tris[2-(2-methoxyethoxy)ethyl]amine,4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane,dicyclohexano-24-crown-8, dicyclohexano-18-crown-6,18-Crown-6,dibenzo-24-crown-8,dibenzo-18-crown-6,15-crown-5,1-aza-15-crown-5,12-crown-4,tetrabutylphosphonium bromide, tetrabutylphosphonium chloride andtributylhexadecylphosphonium bromide. Combinations comprising at leastone of the foregoing catalysts can be used.

Specific examples of suitable second solvents include but are notlimited to toluene, xylene, dichloromethane, dichloroethane, chloroform,chlorobenzene, ortho dichlorobenzene, trichlorobenzene,dimethylformamide, diethylacetamide, tetrahydrofuran, dimethylsulfoxide,or combinations comprising at least one of the foregoing solvents. Theamount of second solvent employed in the reaction of compound of Formula(VI) with the hydroxy compound of Formula (VII) can be about 5 moles toabout 100 moles per mole of the compound of Formula (VI). Within thisrange the amount may be greater than or equal to about 10 moles, or,more specifically, greater than or equal to about 20 moles. Also withinthis range the amount may be less than or equal to about 90 moles, or,more specifically, less than or equal to about 80 moles. In certainembodiments the hydroxy compound of Formula (VII) may be used inaddition to or instead of the second solvent. In this embodiment theamount of the hydroxy compound present in the reaction can be 5 moles to105 moles per mole of the compound of Formula (VI).

The temperature of the reaction of the compound of Formula (VI) with thehydroxy compound of Formula (VII) can be about 80° C. to about 180° C.Within this range the temperature may be greater than or equal to about90° C., or, more specifically, greater than or equal to about 100° C.Also within this range the temperature may be less than or equal toabout 160° C., or, more specifically, less than or equal to about 150°C. The time for the reaction of compound of Formula (VI) with thehydroxy compound of Formula (VII) can be about 4 hours to about 15hours. Within this range the time may be greater than or equal to about6 or, more specifically, greater than or equal to about 8 hours. Alsowithin this range the time may be less than or equal to about 14 hours,or, more specifically, less than or equal to about 12 hours.

A polymer composition is also disclosed herein, said compositioncomprising a polymer and a compound of Formula (I) as described aboveand or a compound of Formula (VIII)

wherein R⁹, R¹⁹, and R¹¹ are independently at each occurrence hydrogen,a halogen, a cyano functionality, a C₁-C₂₀ aliphatic functionality, aC₃-C₁₀ cycloaliphatic functionality or a C₃-C₂₀ aromatic functionality;R⁴ and R⁵ are independently at each occurrence hydrogen, a halogen, acyano functionality, a C₁-C₂₀ aliphatic functionality, a C₃-C₁₀cycloaliphatic functionality or a C₃-C₁₀ aromatic functionality; R⁷ andR⁸ are independently at each occurrence, a halogen, a cyanofunctionality, a C₁-C₂₀ aliphatic functionality, a C₃-C₁₀ cycloaliphaticfunctionality or a C₃-C₁₀ aromatic functionality; R⁶ is a C₂-C₂₀aliphatic functionality, a C₃-C₁₀ cycloaliphatic functionality or aC₃-C₂₀ aromatic functionality, “n” and “m” are each independentlyintegers having a value of 1 to 3 and a polymer.

In one embodiment, R¹, R², R³, R⁴, and R⁵ are independently at eachoccurrence hydrogen or a C₂-C₆ aliphatic functionality, R⁷ and R⁸ areindependently at each occurrence a halogen, a cyano functionality, or aC₁-C₆ aliphatic functionality, and n and m are each 0 to 3.

The compounds may be prepared in a similar manner as described for thepreparation of the compound of Formula (I).

The compounds of Formulas (I) and (VIII) can have utility as fluorescentbrighteners. In one embodiment, a compound that can be used as afluorescent brightener has an absorption maximum in the 300 to 400 nmrange, and an emission maximum in the 400 to 500 nm range, measured inan appropriate solvent, such as dichloromethane. Fluorescent brightenersfind utility as an additive to a wide range of materials, includingtextiles, paper, detergents, and polymers. For example fluorescentbrighteners can be used to impart a “whiter-than-white” appearance topolymers pigmented with titanium dioxide; to produce a bluish tinge inclear polymers, masking yellowness; to make lightly colored polymersappear more brilliant; and/or to aid in restoring whiteness to recycledpolymers.

One or more of the foregoing effects can be observed with the naked eye,or measured using a tristimulus reflection colorimeter, using the CIELABcolor scale, L*, a*, and b*, where L* defines lightness, the a* axisdenotes green/red (+/−) and the b* axis defines blue/yellow (+/−).Higher L* values indicate that more light is reflected. Addition offluorescent brighteners can result in lower b* values. The blue colorrange occupies the negative (−) side of the b* axis, while the yellowcolor range occupies the positive side. The lower the b* value, the lessyellow color is perceived by the naked eye, and likewise, lower b*values indicate greater perception of whiteness and blue color.Accordingly, when used as fluorescent brighteners, the compounds ofFormula (I) decrease the b* value of the composition containing acompound of Formulas (I) relative to the same composition without thecompound of Formula (I). In one embodiment the b* value of thecomposition containing the compound of Formula (I) is decreased by atleast 5% of the b* value of the same composition without the compound ofFormula (I). Similarly, when used as fluorescent brighteners, thecompounds of Formula (VIII) decrease the b* value of the compositioncontaining a compound of Formulas (VIII) relative to the samecomposition without the compound of Formula (VIII). In one embodimentthe b* value of the composition containing the compound of Formula(VIII) is decreased by at least 5% of the b* value of the samecomposition without the compound of Formula (VIII).

Both of the compounds of Formula (I) and (VIII) (singly or incombination) can be used in the brightening of polymers, especiallythermoplastic polymers, for example, polycarbonates, polyesters,polyimides, polyamides, polyetherimides, thermoplastic polyurethanes,epoxide containing polymers, polyvinylchlorides, and others. It is alsopossible to use combinations comprising one or more of foregoingpolymers, for example combinations of polycarbonates and/orpolycarbonate copolymers with polyamides, polyesters, otherpolycarbonates; copolyester-polycarbonates, olefin polymers such asacrylonitrile-butadiene-styrene (ABS), polystyrene, polyethylene;polysiloxanes, polysilanes and/or polysulfones. As used herein, a“combination” is inclusive of all mixtures, blends, and alloys. When thecombination is with a non-thermoplastic polymer, in certain embodimentsthe non-thermoplastic polymer(s) may be present in an amount of lessthan or equal to 40 weight percent, more specifically less than or equalto 35 weight percent and most specifically less than or equal to about30 weight percent, based on the total weight of the polymer composition.

When used as an fluorescent brightener in a polymer composition, thecompounds of Formula (I) and/or (VIII) can be present in an amount ofabout 0.05 weight percent to about 20 weight percent, based on the totalweight of the composition.

In addition to the polymer, the polymer composition may include variousadditives ordinarily incorporated in resin compositions of this type,with the proviso that the additives are preferably selected so as to notsignificantly adversely affect the desired properties of thethermoplastic composition. Mixtures of additives may be used. Theamounts of such additives will depend on the desired properties of thecomposition, and are readily determinable by one of ordinary skill inthe art without undue experimentation.

Exemplary additives include such materials as fillers or reinforcingagents, thermal stabilizers, radiation stabilizers, antioxidants, lightstabilizers, ultraviolet (UV) light stabilizers, plasticizers, visualeffect enhancers, extenders, antistatic agents, catalyst quenchers, moldrelease agents, flame retardants, infrared shielding agents, whiteningagents, blowing agents, anti-drip agents, impact modifiers andprocessing aids. The different additives that can be incorporated in thepolymer compositions of the present invention are typically commonlyused and known to those skilled in the art.

Suitable fillers or reinforcing agents include, for example, silicatesand silica powders such as aluminum silicate (mullite), syntheticcalcium silicate, zirconium silicate, fused silica, crystalline silicagraphite, natural silica sand, or the like; boron powders such asboron-nitride powder, boron-silicate powders, or the like; oxides suchas TiO₂, aluminum oxide, magnesium oxide, or the like; calcium sulfate(as its anhydride, dihydrate or trihydrate); calcium carbonates such aschalk, limestone, marble, synthetic precipitated calcium carbonates, orthe like; talc, including fibrous, modular, needle shaped, lamellartalc, or the like; wollastonite; surface-treated wollastonite; glassspheres such as hollow and solid glass spheres, silicate spheres,cenospheres, aluminosilicate (armospheres), or the like; kaolin,including hard kaolin, soft kaolin, calcined kaolin, kaolin comprisingvarious coatings known in the art to facilitate compatibility with thepolymeric matrix resin, or the like; single crystal fibers or “whiskers”such as silicon carbide, alumina, boron carbide, iron, nickel, copper,or the like; fibers (including continuous and chopped fibers) such asasbestos, carbon fibers, glass fibers, such as E, A, C, ECR, R, S, D, orNE glasses, or the like; sulfides such as molybdenum sulfide, zincsulfide or the like; barium compounds such as barium titanate, bariumferrite, barium sulfate, heavy spar, or the like; metals and metaloxides such as particulate or fibrous aluminum, bronze, zinc, copper andnickel or the like; flaked fillers such as glass flakes, flaked siliconcarbide, aluminum diboride, aluminum flakes, steel flakes or the like;fibrous fillers, for example short inorganic fibers such as thosederived from blends comprising at least one of aluminum silicates,aluminum oxides, magnesium oxides, and calcium sulfate hemihydrate orthe like; natural fillers and reinforcements, such as wood flourobtained by pulverizing wood, fibrous products such as cellulose,cotton, sisal, jute, starch, cork flour, lignin, ground nut shells,corn, rice grain husks or the like; organic fillers such aspolytetrafluoroethylene; reinforcing organic fibrous fillers formed fromorganic polymers capable of forming fibers such as poly(ether ketone),polyimide, polybenzoxazole, poly(phenylene sulfide), polyesters,polyethylene, aromatic polyamides, aromatic polyimides, polyetherimides,polytetrafluoroethylene, acrylic resins, poly(vinyl alcohol) or thelike; as well as additional fillers and reinforcing agents such as mica,clay, feldspar, flue dust, fillite, quartz, quartzite, perlite, tripoli,diatomaceous earth, carbon black, or the like, or combinationscomprising at least one of the foregoing fillers or reinforcing agents.

The fillers and reinforcing agents may be coated with a layer ofmetallic material to facilitate conductivity, or surface treated withsilanes to improve adhesion and dispersion with the polymeric matrixresin. In addition, the reinforcing fillers may be provided in the formof monofilament or multifilament fibers and may be used either alone orin combination with other types of fiber, through, for example,co-weaving or core/sheath, side-by-side, orange-type or matrix andfibril constructions, or by other methods known to one skilled in theart of fiber manufacture. Suitable cowoven structures include, forexample, glass fiber-carbon fiber, carbon fiber-aromatic polyimide(aramid) fiber, and aromatic polyimide fiberglass fiber or the like.Fibrous fillers may be supplied in the form of, for example, rovings,woven fibrous reinforcements, such as 0-90 degree fabrics or the like;non-woven fibrous reinforcements such as continuous strand mat, choppedstrand mat, tissues, papers and felts or the like; or three-dimensionalreinforcements such as braids.

Suitable thermal stabilizer additives include, for example,organophosphites such as triphenyl phosphite,tris-(2,6-dimethylphenyl)phosphite, tris-(mixed mono- anddi-nonylphenyl)phosphite; phosphonates such as dimethylbenzenephosphonate, phosphates such as trimethyl phosphate, and combinationscomprising at least one of the foregoing heat stabilizers.

Non-limiting examples of antioxidants that can be used in the polymercompositions include tris(2,4-di-tert-butylphenyl)phosphite;3,9-di(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane;3,9-di(2,4-dicumylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane;tris(p-nonylphenyl)phosphite;2,2′,2″-nitrilo[triethyl-tris[3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2′-diyl]phosphite];3,9-distearyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane;dilauryl phosphite;3,9-di[2,6-di-tert-butyl-4-methylphenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane;tetrakis(2,4-di-tert-butylphenyl)-4,4′-bis(diphenylene)phosphonite;distearyl pentaerythritol diphosphite; diisodecyl pentaerythritoldiphosphite; 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediolphosphite; tristearyl sorbitol triphosphite;tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene diphosphonite;(2,4,6-tri-tert-butylphenyl)-2-butyl-2-ethyl-1,3-propanediolphosphite;triisodecylphosphite; and combinations comprising at least one of theforegoing antioxidants.

Non-limiting examples of UV stabilizers that can be used include2-(2′-hydroxyphenyl)-benzotriazoles, for example, the 5′-methyl-;3′,5′-di-tert.-butyl-; 5′-tert-butyl-; 5′-(1,1,3,3-tetramethylbutyl)-;5-chloro-3′,5′-di-tert-butyl-; 5-chloro-3′-tert.-butyl-5′-methyl-;3′-sec.-butyl-5′-tert.-butyl-; 3′-alpha-methylbenzyl-5′-methyl;3′-alpha-methylbenzyl-5′-methyl-5-chloro-; 4′-hydroxy-; 4′-methoxy-;4′-octoxy-; 3′,5′-di-tert.-amyl-; 3′-methyl-5′-carbomethoxyethyl-; and5-chloro-3′,5′-di-tert-amyl-derivatives; and Tinuvin® 234 (availablefrom Ciba Specialty Chemicals). Also suitable are the2,4-bis-(2′-hydroxyphenyl)-6-alkyl-s-triazines, for example, the6-ethyl-; 6-heptadecyl-; and 6-undecyl-derivatives.2-Hydroxybenzophenones can also be used, for example, the 4-hydroxy-;4-methoxy-; 4-octoxy-; 4-decyloxy-; 4-dodecyloxy-; 4-benzyloxy-;4,2′,4′-trihydroxy-; 2,2′,4,4′-tetrahydroxy- and2′-hydroxy-4,4′-dimethoxy-derivatives.1,3-bis-(2′-Hydroxybenzoyl)-benzenes, for example,1,3-bis-(2′-hydroxy-4′-hexyloxy-benzoyl)-benzene;1,3-bis-(2′-hydroxy-4′-octyloxy-benzoyl)-benzene; and1,3-bis-(2′-hydroxy-4′-dodecyloxybenzoyl)-benzene may also be employed.Esters of optionally substituted benzoic acids, for example,phenylsalicylate; octylphenylsalicylate; dibenzoylresorcin;bis-(4-tert-butylbenzoyl)-resorcin; benzoylresorcin;3,5-di-tert-butyl-4-hydroxybenzoic acid-2,4-di-tert-butylphenyl ester or-octadecyl ester or -2-methyl-4,6-di-tert-butyl ester may likewise beemployed. Acrylates, for example, alpha-cyano-beta, beta-diphenylacrylicacid-ethyl ester or isooctyl ester, alpha-carbomethoxy-cinnamic acidmethyl ester, alpha-cyano-beta-methyl-p-methoxy-cinnamic acid methylester or -butyl ester or N-(beta-carbomethoxyvinyl)-2-methyl-indolinemay likewise be employed. Oxalic acid diamides, for example,4,4′-di-octyloxy-oxanilide;2,2′-di-octyloxy-5,5′-di-tert-butyl-oxanilide;2,2′-di-dodecyloxy-5,5-di-tert-butyl-oxanilide;2-ethoxy-2′-ethyl-oxanilide;N,N′-bis-(3-dimethyl-aminopropyl)-oxalamide;2-ethoxy-5-tert-butyl-2′-ethyloxanilide and the mixture thereof with2-ethoxy-2′-ethyl-5,4′-di-tert-butyl-oxanilide; or mixtures of ortho-and para-methoxy- as well as of n- and p-ethoxy-disubstituted oxanilidesare also suitable as UV stabilizers. Preferably the ultraviolet lightstabilizer is 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole;2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;2-[2-hydroxy-3,5-di-(alpha,alpha-dimethylbenzyl)phenyl]-2H-benzotriazole;2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;2-hydroxy-4-octyloxybenzophenone; nickel bis(O-ethyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate);2,4-dihydroxybenzophenone;2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole; nickelbutylamine complex with 2,2′-thiobis(4-tert-butylphenol);2-ethoxy-2′-ethyloxanilide; and2-ethoxy-2′-ethyl-5,5′-ditert-butyloxanilide. Combinations comprising atleast one of the foregoing UV stabilizers can be used.

Plasticizers, lubricants, and/or mold release agents additives may alsobe used. There is considerable overlap among these types of materials,which include, for example, phthalic acid esters such asdioctyl-4,5-epoxy-hexahydrophthalate;tris-(octoxycarbonylethyl)isocyanurate; tristearin; di- orpolyfunctional aromatic phosphates such as resorcinol tetraphenyldiphosphate (RDP), the bis(diphenyl) phosphate of hydroquinone and thebis(diphenyl) phosphate of bisphenol-A; poly-alpha-olefins; epoxidizedsoybean oil; silicones, including silicone oils; esters, for example,fatty acid esters such as alkyl stearyl esters, for example, methylstearate; stearyl stearate and pentaerythritol tetrastearate, mixturesof methyl stearate and hydrophilic and hydrophobic nonionic surfactantscomprising polyethylene glycol polymers, polypropylene glycol polymers,and copolymers thereof, for example, methyl stearate andpolyethylene-polypropylene glycol copolymers in a suitable solvent; andwaxes such as beeswax, montan wax, paraffin wax. Combinations comprisingat least one of the foregoing materials can be used.

Visual effect enhancers, sometimes known as visual effects additives orpigments or colorants may be present in an encapsulated form, anon-encapsulated form, or laminated to a particle comprising polymericresin. Some non-limiting examples of visual effects additives arealuminum, gold, silver, copper, nickel, titanium, stainless steel,nickel sulfide, cobalt sulfide, manganese sulfide, metal oxides, whitemica, black mica, pearl mica, synthetic mica, mica coated with titaniumdioxide, metal-coated glass flakes, and colorants, including but notlimited, to Perylene Red. The visual effect additive may have a high orlow aspect ratio and may comprise greater than 1 facet. Dyes may beemployed such as Solvent Blue 35, Solvent Blue 36, Disperse Violet 26,Solvent Green 3, Anaplast Orange LFP, Perylene Red, and Morplas Red 36.Fluorescent dyes may also be employed including, but not limited to,Permanent Pink R (Color Index Pigment Red 181, from ClariantCorporation), Hostasol Red 5B (Color Index #73300, CAS #522-75-8, fromClariant Corporation) and Macrolex Fluorescent Yellow 10GN (Color IndexSolvent Yellow 160:1, from Bayer Corporation). Pigments such as titaniumdioxide, zinc sulfide, carbon black, cobalt chromate, cobalt titanate,cadmium sulfides, iron oxide, sodium aluminum sulfosilicate, sodiumsulfosilicate, chrome antimony titanium rutile, nickel antimony titaniumrutile, and zinc oxide may be employed. Combinations comprising at leastone of the foregoing visual effects additives can be used. Visual effectadditives in encapsulated form usually comprise a visual effect materialsuch as a high aspect ratio material like aluminum flakes encapsulatedby a polymer. The encapsulated visual effect additive can have the shapeof a bead.

The term “antistatic agent” refers to monomeric, oligomeric, orpolymeric materials that can be processed into polymer resins and/orsprayed onto materials or articles to improve conductive properties andoverall physical performance. Examples of monomeric antistatic agentsinclude glycerol monostearate, glycerol distearate, glyceroltristearate, ethoxylated amines, primary, secondary and tertiary amines,ethoxylated alcohols, alkyl sulfates, alkylarylsulfates,alkylphosphates, alkylaminesulfates, alkyl sulfonate salts such assodium stearyl sulfonate, sodium dodecylbenzenesulfonate, quaternaryammonium salts, quaternary ammonium resins, imidazoline derivatives,sorbitan esters, ethanolamides, betaines, and combinations comprising atleast one of the foregoing monomeric antistatic agents.

Exemplary polymeric antistatic agents include certain polyesteramides,polyether-polyamide (polyetheramide) block copolymers,polyetheresteramide block copolymers, polyetheresters, or polyurethanes,each containing polyalkylene oxide units that may be polyalkylene glycolmoieties, for example, polyethylene glycol, polypropylene glycol andpolytetramethylene glycol. Such polymeric antistatic agents arecommercially available, such as, for example, Pelestat™ 6321 (Sanyo),Pebax™ H1657 (Atofina), and Irgastat™ P18 and P22 (Ciba-Geigy). Otherpolymeric materials that may be used as antistatic agents are inherentlyconducting polymers such as polyaniline (commercially available asPANIPOL®EB from Panipol), polypyrrole and polythiophene (commerciallyavailable from Bayer), which retain some of their intrinsic conductivityafter melt processing at elevated temperatures. Combinations comprisingat least one of the foregoing polymeric antistatic agents can be used.In one embodiment, carbon fibers, carbon nanofibers, carbon nanotubes,carbon black, or any combination of the foregoing may be used in apolymeric resin containing chemical antistatic agents to render thecomposition electrostatically dissipative.

Non-limiting examples of mold release compositions, combinations ofwhich can be used, include esters of long-chain aliphatic acids andalcohols such as pentaerythritol, guerbet alcohols, long-chain ketones,siloxanes, alpha.-olefin polymers, long-chain alkanes and hydrocarbonshaving 15 to 600 carbon atoms.

Non-limiting examples of flame retardants that can be used includepotassium diphenylsulfone sulfonate, perfluoroalkane sulfonates, thephosphite esters of polyhydric phenols such as resorcinol and bisphenolA, and combinations comprising at least one of the foregoing flameretardants.

The thermoplastic composition may optionally comprise an impactmodifier. The impact modifier may be added to the thermoplasticcomposition in an amount of about 1 percent to about 30 percent byweight, based on the total weight of the composition. Suitable impactmodifiers include those comprising one of several different rubberymodifiers such as graft or core shell rubbers or combinations comprisingat least one of these modifiers. Impact modifiers are illustrated byacrylic rubber, ASA rubber, diene rubber, organosiloxane rubber,ethylene propylene diene monomer (EPDM) rubber,styrene-butadiene-styrene (SBS) rubber,styrene-ethylene-butadiene-styrene (SEBS) rubber,acrylonitrile-butadiene-styrene (ABS) rubber,methacrylate-butadiene-styrene (MBS) rubber, styrene acrylonitrilecopolymer and glycidyl ester impact modifier.

Non-limiting examples of processing aids that can be used includeDoverlube® FL-599 (available from Dover Chemical Corporation),Polyoxyter® (available from Polychem Alloy Inc.), Glycolube® P(available from Lonza Chemical Company), pentaerythritol tetrastearate,Metablen® A-3000 (available from Mitsubishi Rayon) and neopentyl glycoldibenzoate.

Radiation stabilizers may also be present in the thermoplasticcomposition, specifically gamma-radiation stabilizers. Suitablegamma-radiation stabilizers include diols, such as ethylene glycol,propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol,meso-2,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 1,4-pentanedioland 1,4-hexandiol; alicyclic alcohols such as 1,2-cyclopentanediol and1,2-cyclohexanediol; branched acyclic diols such as2,3-dimethyl-2,3-butanediol (pinacol), and polyols, as well asalkoxy-substituted cyclic or acyclic alkanes. Alkenols with sites ofunsaturation are also a useful class of alcohols, examples of whichinclude 4-methyl-4-penten-2-ol, 3-methyl-pentene-3-ol,2-methyl-4-penten-2-ol, 2,4-dimethyl-4-penten-2-ol, and 9-decen-1-ol.Another class of suitable alcohols is the tertiary alcohols, which haveat least one hydroxy substituted tertiary carbon. Examples of theseinclude 2-methyl-2,4-pentanediol (hexylene glycol), 2-phenyl-2-butanol,3-hydroxy-3-methyl-2-butanone and cycloaliphatic tertiary carbons suchas 1-hydroxy-1-methyl-cyclohexane. Another class of suitable alcohols ishydroxymethyl aromatics, which have hydroxy substitution on a saturatedcarbon attached to an unsaturated carbon in an aromatic ring. Thehydroxy substituted saturated carbon may be a methylol group (—CH₂OH) orit may be a member of a more complex hydrocarbon group such as would bethe case with (—CR⁷HOH) or (—CR₂ ⁷OH) wherein R⁷ is a complex or asimply hydrocarbon. Specific hydroxy methyl aromatics may be benzhydrol,1,3-benzenedimethanol, benzyl alcohol, 4-benzyloxy benzyl alcohol andbenzyl alcohol. Specific alcohols are 2-methyl-2,4-pentanediol (alsoknown as hexylene glycol), polyethylene glycol, polypropylene glycol.

Where a foam is desired, a blowing agent may be added to thecomposition. Suitable blowing agents include for example, low boilinghalohydrocarbons; those that generate carbon dioxide; blowing agentsthat are solid at room temperature and that when heated to temperatureshigher than their decomposition temperature, generate gases such asnitrogen, carbon dioxide, ammonia gas or the like, such asazodicarbonamide, metal salts of azodicarbonamide, 4,4′oxybis(benzenesulfonylhydrazide), sodium bicarbonate, ammoniumcarbonate, or the like, or combinations comprising at least one of theforegoing blowing agents.

Anti-drip agents may also be used, for example a fibril forming ornon-fibril forming fluoropolymer such as polytetrafluoroethylene (PTFE).The anti-drip agent may be encapsulated by a rigid copolymer asdescribed above, for example styrene-acrylonitrile copolymer (SAN). PTFEencapsulated in SAN is known as TSAN. Encapsulated fluoropolymers may bemade by polymerizing the encapsulating polymer in the presence of thefluoropolymer, for example an aqueous dispersion. TSAN may providesignificant advantages over PTFE, in that TSAN may be more readilydispersed in the composition. A suitable TSAN may comprise, for example,about 50 wt. percent PTFE and about 50 wt. percent SAN, based on thetotal weight of the encapsulated fluoropolymer. The SAN may comprise,for example, about 75 wt. percent styrene and about 25 wt. percentacrylonitrile based on the total weight of the copolymer. Alternatively,the fluoropolymer may be pre-blended in some manner with a secondpolymer, such as for, example, an aromatic polycarbonate resin or SAN toform an agglomerated material for use as an anti-drip agent. Eithermethod may be used to produce an encapsulated fluoropolymer.

The thermoplastic polymer compositions may be manufactured by methodsgenerally available in the art, for example, in one embodiment, powderedpolymer resin and/or other optional components are first blended, forexample in a Henschel™ high speed mixer. Other low shear processesincluding but not limited to hand mixing may also accomplish thisblending. The blend is then fed into the throat of a twin-screw extrudervia a hopper. Alternatively, one or more of the components may beincorporated into the composition by feeding directly into the extruderat the throat and/or downstream through a sidestuffer. Such additivesmay also be compounded into a masterbatch with a desired polymeric resinand fed into the extruder. The extruder is generally operated at atemperature higher than that necessary to cause the composition to flow.The extrudate is immediately quenched in a water batch and pelletized.The pellets may be one-fourth inch long (6.35 millimeter) or less asdesired. Such pellets may be used for subsequent molding, shaping, orforming.

Shaped, formed, or molded articles comprising the polymer compositionsare also provided. The polymer compositions may be molded into usefulshaped articles by a variety of means such as injection molding,extrusion, rotational molding, blow molding and thermoforming to formarticles such as, for example, computer and business machine housingssuch as housings for monitors, handheld electronic device housings suchas housings for cell phones, electrical connectors, and components oflighting fixtures, ornaments, home appliances, roofs, greenhouses, sunrooms, swimming pool enclosures and automotive applications, for exampleforward lighting enclosures for car headlamps).

The disclosure is explained in more detail with reference to thefollowing non-limiting Examples.

The reagents used for the present study are laboratory reagent gradesand were used without further purifications. Sources for the reagentswere as follows: 4-Bromonaphthalic anhydride (Anshan Huifeng ChemicalCo. Ltd. China), Acetic acid (S.D. Fine. Chem., Min. assay 99%), Aniline(S.D. Fine. Chem., Min. assay 98%), Diethyl aniline (Aldrich Chemicals,purity 98.00%), Ethylene glycol (S.D. Fine. Chem., Min. assay 98.0%),Propylene glycol, (S.D. Fine chem., India, min. assay 99%), Butane diol(Aldrich Chemicals, purity 99.00), Sodium Hydroxide (S.D. Fine. Chem.,Min. assay 99%), UVITEX® OB (Ciba Specialty Chemicals).

TLC using the eluent system ethyl acetate:n-Hexane (10:90) was used tomonitor progress of reactions.

Structure was determined using ¹H-NMR on a Bruker 300 MHzspectrophotometer.

HPLC data were obtained using Shimadzu HPLC Class-VP instrument and RPXterra column-C₁₈ (a HPLC column manufactured by Waters, USA), 4.6×50millimeters (mm), 5 micrometers (μm).

TGA analyses were carried out using a TGA 2950 instrument equipped withan auto sampler, and available from TA Instruments.

The UV-VIS spectral characteristics of the fluorescent whiteners (lambdamaximum (λ_(max)) absorption) were measured in dichloromethane in thewavelength region of 300 nm to 800 nm using a double beam UV/VISPerkin-Elmer Lambda 900 UV/VIS/NIR spectrophotometer.

Fluorescence properties of fluorescent whiteners (lambda maximum(λ_(max)) emission, were evaluated using Hitachi-F-4500spectrophotometer. Molded chips of 1 mm thickness containing 0.005% ofcompound of Formulas (I) or (VIII) along with polycarbonate were used todetermine fluorescence properties.

Example 1

This example describes the preparation of2-(2,6-diisopropyl-phenyl)-6-(2-hydroxyethoxy)-benzo[de]isoquinoline-1,3-dionein two steps.

Step A: Preparation of N-(2,6-diisopropyl phenyl)-4-bromo naphthalimide

A mixture of 4-bromo-1,8-naphthalic anhydride (10 g (grams)),2,6-diisopropylaniline (6.74 g) and acetic acid (75 milliliters (ml))was heated under reflux with stirring for 10 (hrs (hours)). The reactionmixture was cooled to room temperature and filtered. The solids obtainedwere washed first with acetic acid and then with water, and dried at120° C. for 8 hrs to obtain 13.1 g of the product.

Step B: Preparation of2-(2,6-diisopropyl-phenyl)-6-(2-hydroxy-ethoxy)-benzo[de]isoquinoline-1,3-dione

A mixture of N-(2,6-diisopropyl phenyl)-4-bromo naphthalimide (4.0 grams(g)), sodium hydroxide (0.54 g), and 1,2-ethylene glycol (50 milliliters(ml)) was stirred at 120° C. for 10 hrs. The reaction mixture was cooledto room temperature, 100 ml water was added to the mixture, and theseparated solid was filtered, washed with water, and dried at 100° C.for 8 hrs to obtain the crude product in a yield of 2.25 g. The crudeproduct was further purified using column chromatography in an eluentsystem consisting of ethyl acetate and n-hexane mixture (20:80). ¹H-NMR:1.06 δ (d, 12 protons); 2.63 δ (m, 2 proton); 3.92 δ (m, 2 protons);4.38 δ (triplet, 2 protons); 5.14 δ (Triplet, 1 proton); 7.36 δ (m, 4protons); 7.88 δ (m, 1 protons); 8.54 δ (Triplet, 2 protons); 8.76 δ (d,1 protons); Mass (M+): 418.

Example 2

This example describes the preparation of2-(2,6-diisopropyl-phenyl)-6-(3-hydroxypropoxy)-benzo[de]isoquinoline-1,3-dione.

A mixture of N-(2,6-diisopropylphenyl)-4-bromo naphthalimide (4.0 g, asprepared in Step A of example 1), sodium hydroxide (0.54 g) and1,3-propane diol (50 ml) was stirred at 120° C. for 10 hrs. The reactionmixture was cooled to room temperature, 100 ml water was added to themixture, and the separated solid was filtered, washed with water, anddried at 100° C. for 8 hrs to obtain the crude product in a yield of 3.1g. The crude product was further purified using column chromatography inan eluent system consisting of ethyl acetate and n-hexane mixture(20:80). ¹H-NMR: 1.18 δ (d, 12 protons); 2.01 δ (s, 1 proton); 2.25 δ(m, 2 protons); 3.96 δ (m, 2 protons); 4.47 δ (m, 2 proton); 7.13 δ (m,1 protons); 7.34 δ (m, 2 protons); 7.48 δ (m, 1 protons); 7.76 δ (m, 1protons); 8.65 δ (m, 3 protons).

Example 3

This example describes the preparation of2-(2,6-diisopropyl-phenyl)-6-(4-hydroxy-butoxy)-benzo[de]isoquinoline-1,3-dione.

A mixture of N-(2,6-diisopropyl phenyl)-4-bromo naphthalimide (4.0 g asprepared in Step A of example 1), sodium hydroxide (0.54 g) and1,3-butane diol (50 ml) was stirred at 120° C. for 10 hrs. The reactionmixture was cooled to room temperature, 100 ml water was added to themixture, and the separated solid was filtered, washed with water, anddried at 100° C. for 8 hrs to obtain the crude product in a yield of 3.1g. The crude product was further purified using column chromatography inan eluent system consisting of ethyl acetate and n-hexane mixture(20:80). ¹H-NMR: 1.17 δ (m, 12 protons); 1.68 δ (s, 1 proton); 1.90 δ(m, 2 protons); 2.12 δ (m, 2 protons); 2.76 δ (m, 2 proton); 3.82 δ (m,2 protons); 4.38 δ (m, 2 protons); 7.343 δ (m, 4 protons); 7.77 δ (m, 1protons); 8.69 δ (m, 3 protons).

Example 4

This example describes the preparation2-(2,6-diisopropyl-phenyl)-6-[4-(1-methyl-1-phenyl-ethyl)-phenoxy]-benzo[de]isoquinoline-1,3-dione.

A mixture of N-(2,6-diisopropyl phenyl)-4-bromonaphthalimide (4.0 g),potassium hydroxide (0.77 g) and dimethylformamide (30 ml), 18-crown-6(0.02 g), and p-cumylphenol (3.89 g) was stirred at 50° C. for 6 hours.The reaction mixture was cooled to room temperature, 100 ml water wasadded to the mixture, and the separated solid was filtered, washed withwater and dried at 60° C. for 8 hrs to obtain the crude product in ayield of (5.0 g). The crude product was further purified by carrying outcolumn chromatography (silica gel 60-120 mesh) using ethyl acetate andn-hexane mixture (20:80). H-NMR: 1.18 δ (m, 12 protons); 1.79 δ (s, 6proton); 2.79 δ (m, 2 protons); 7.34 δ (m, 14 protons); 7.83 δ (m, 1protons); 8.56 δ (m, 1 protons); 8.79 δ (m, 2 proton).

Example 5

This example describes the preparation of6-(2-hydroxy-ethoxy)-2-p-tolyl-benzo[de]isoquinoline-1,3-dione.

Step A: Preparation of 6-bromo-2-p-tolyl-benzo[de]isoquinoline-1,3-dione

A mixture of 4-Bromo 1,8 naphthalic anhydride (10 g), p-toluidine (4.08g) and acetic acid (75 ml) was refluxed with stirring for 10 hours.Water (200 ml) was added at room temperature, the separated solid wasfiltered, washed with acetic acid followed by water and dried at 100° C.for 8 hours to yield 11.5 g of the product.

Step B: 6-(2-hydroxy-ethoxy)-2-p-tolyl-benzo[de]isoquinoline-1,3-dione

A mixture of 6-bromo-2-p-tolyl-benzo[de]isoquinoline-1,3-dione (4.0 g),sodium hydroxide (0.65 g), and 1,2-ethylene glycol (50 ml) wasmaintained under reflux with stirring at 120° C. for 10 hrs. Thereaction mixture was then cooled to room temperature and water (100 ml)was added to the mixture. The solid that separated out was filtered,washed with water, and dried at 100° C. for 8 hours (Yield=2.71 g). Thecrude product was purified using 120 ml monochlorobenzene and 0.25 gactivated charcoal to obtain pure product weighing 1.32 g. H¹-NMR: 2.39δ (s, 3 protons); 3.92 δ (m, 2 proton); 4.35 δ (t, 2 protons); 5.13 δ(t, 1 proton); 7.22 δ (m, 2 protons); 7.31 δ (m, 3 protons); 7.83 δ (t,1 proton); 8.44 δ (m, 2 protons); 8.68 δ (d, 1 proton).

Example 6

This example describes the preparation of6-(3-hydroxy-propoxy)-2-phenyl-benzo[de]isoquinoline-1,3-dione.

Step A: Preparation of 6-bromo-2-phenyl-benzo[de]isoquinoline-1,3-dione

A mixture of 4-bromo-1,8-naphthalic anhydride (10 g), aniline (3.54 g)and acetic acid (75 ml) was refluxed with stirring for 10 hrs. Thereaction mixture was then cooled to room temperature, whereupon solidseparated out. The solid was filtered, washed with water (50 ml)followed by acetic acid (50 ml) and dried at 100° C. for 8 hours(Yield=10.8 gm).

Step B: Preparation of6-(3-Hydroxy-propoxy)-2-phenyl-benzo[de]isoquinoline-1,3-dione

A mixture of 6-bromo-2-phenyl-benzo[de]isoquinoline-1,3-dione (4.0 g),sodium hydroxide (0.67 g) and 1,3-propane diol (50 ml) was maintainedwith stirring at 120° C. for 10 hrs. The reaction mixture was cooled toroom temperature. Water (100 ml) was added to the mixture and solidseparated out. The solid was filtered, washed with water, and dried at100° C. for 8 hours to provide a crude product in a yield of 1.90 g. Thecrude product was purified using mono chloro benzene (60 ml) andactivated charcoal (0.20 g). The weight of the of the purified productobtained was 1.15 g. ¹H-NMR: 3.93 δ (m, 2 protons); 4.35 δ (m, 1proton); 2.25 δ (m, 2 protons); 3.96 δ (m, 2 protons); 4.47 δ (m, 2proton); 7.13 δ (m, 2 protons); 5.14 δ (m, 1 proton); 7.36 δ (m, 3protons); 7.51 δ (m, 3 protons); 7.84 δ (m, 1 proton); 8.46 δ (m, 2protons); 8.69 δ (m, 1 proton).

Example 7

This example describes the preparation of6-(2-hydroxy-ethoxy)-2-phenyl-benzo[de]isoquinoline-1,3-dione.

A mixture of 6-bromo-2-phenyl-benzo[de]isoquinoline-1,3-dione (2.0 g;prepared in step A of Example 5), sodium hydroxide (0.34 g) and1,2-ethylene glycol (25 ml) was maintained with stirring at 120° C. for10 hrs. The reaction mixture was cooled to room temperature, water (100ml) was added to the mixture and solid separated out. The solid wasfiltered, washed with water, and dried at 100° C. for 8 hours to providea crude product in a yield of 1.80 g. ¹H-NMR: 2.07 δ (m, 2 protons);3.70 δ (m, 2 proton); 4.42 δ (t, 2 protons); 4.68 δ (t, 1 proton); 7.35δ (m, 3 protons); 7.50 δ (m, 3 protons); 7.83 δ (t, 1 proton); 8.46 δ(m, 2 protons); 8.58 δ (d, 1 proton).

A summary of the above results for Examples 1-7 is shown in Table 1below.

TABLE 1 4-bromo Amount of Sodium Purified Percent Example naphthalimideHydroxy hydroxide Yield Purity No. derivative (g) Hydroxy compoundcompound (g) (g) (HPLC) 1 4 1,2-ethylene glycol 50 ml 0.54 2.25 97.48 24 1,3-propane diol 50 ml 0.54 3.10 97.83 3 4 1,4-butane diol 50 ml 0.542.00 93.0 4 4 p-cumyl phenol 3.89 g 0.77^(a) g 5.00^(b) NA 5 41,2-ethylene glycol 50 ml 0.65 1.32 98.03 6 4 1,3-propane diol 50 ml0.67 1.90 97.3 7 2 1,2-ethylene glycol 25 ml 0.34 1.80 97.3^(a)Potassium hydroxide ^(b)Crude yield NA not available

Characterization of Examples 1-7 and Comparative Example 1 (CE-1)

This example is a comparative study of the properties of a commerciallyavailable fluorescence brightener, UVITEX®-OB (Comparative Example 1)and Examples 1-7 above.

The samples were tested for Tg, lambda max absorption, and emissionvalues. Results are shown in Table 2.

TABLE 2 λ max Absorption λ max Emission Tg at % weight Example No.(nanometers) (nanometers) loss 1 364 419.0 320 2 366 426.0 310 3 366421.0 350 4 366 418.4 350 5 364 420.0 350 6 365 429.0 370 7 364 420.0350 CE-1 375 437.0 310

The results provided in Table 2 indicate that the compounds of Formula(I) and Formula (VIII) absorb and emit at relatively lower wavelengthsthan the commercially available fluorescent brightener UVITEX® OB. Tg at10 percent weight loss is a measure that indicates the temperature atwhich the compounds begin to decompose, and refers to the temperature atwhich the sample has a 10 percent loss in weight compared to the initialamount of sample used for measuring the glass transition temperature(Tg).

While typical embodiments have been set forth for the purpose ofillustration, the foregoing descriptions should not be deemed to be alimitation on the scope herein. Accordingly, various modifications,adaptations, and alternatives may occur to one skilled in the artwithout departing from the spirit and scope herein.

1. A process comprising reacting an anhydride compound of Formula (IV)with an aniline compound of Formula (V)

in the presence of a first solvent to provide a compound of Formula (VI)

wherein R¹, R⁴, and R⁵ are hydrogen, R² and R³ are each t-butyl, R⁷ andR⁸ are independently at each occurrence a halogen, a cyanofunctionality, or a C₁-C₆ functionality, “n” and “m” are each zero, andX is a halogen selected from chlorine or bromine; and reacting thecompound of Formula (VI) with a compound of Formula (VII)R⁶—OH  (VII) in the presence of a base and a second solvent to provide acompound of Formula (I)

wherein R¹, R², R³, R⁴, R⁵, R⁷, R⁸, “n”, and “m” have the same meaningas defined above, and R⁶ is a C₂-C₄ aliphatic functionality, or a C₃-C₂₀aromatic functionality.
 2. The process of claim 1, wherein the reactingof the anhydride compound of Formula (IV) with the aniline compound ofFormula (V) is carried out at a temperature of about 80° C. to about180° C.
 3. The process of claim 1, wherein the reacting of a compound ofFormula (VI) with a hydroxy compound of Formula (VII) is carried out ata temperature of about 80° C. to about 180° C.
 4. The process of claim1, wherein, X is bromine, the first solvent is acetic acid, and thesecond solvent is the hydroxy compound of Formula (VII).
 5. The processof claim 1, wherein the compound of Formula (VII) is para-cumyl phenol.6. The process of claim 1, wherein the compound of Formula (VII) isethylene glycol, propylene glycol, 1,4-butane diol, or a combinationthereof.
 7. The process of claim 1 wherein the compound of Formula (VII)is ethylene glycol.
 8. The process of claim 1, wherein the compound ofFormula (VII) is propylene glycol.
 9. The process of claim 1, whereinthe compound of Formula (VII) is 1,4-butane diol.
 10. The process ofclaim 6, wherein reacting the compound of Formula (VI) with a compoundof Formula (VII) further comprises reacting in the presence of a phasetransfer catalyst.
 11. A composition comprising: a polymer component;and a compound having Formula (II)

wherein “p” is an integer having a value of 2 to
 4. 12. The compositionof claim 11, wherein “p” is an integer having a value of
 2. 13. Thecomposition of claim 11, wherein “p” is an integer having a value of 3.14. The composition of claim 11, wherein “p” is an integer having avalue of
 4. 15. The composition of claim 11, wherein the compound ofFormula (II) is present in an amount of about 0.05 weight percent toabout 20 weight percent, based on the total weight of the composition.16. The composition of claim 11, wherein the polymer component comprisesa polycarbonate.
 17. An article comprising the composition of claim 11.18. A composition comprising: a polymer component; and a compound havingFormula (III)


19. The composition of claim 18, wherein the compound of Formula (II) ispresent in an amount of about 0.05 weight percent to about 20 weightpercent, based on the total weight of the composition.
 20. Thecomposition of claim 18, wherein the polymer component comprises apolycarbonate.
 21. An article comprising the composition of claim 18.